WO2016163244A1 - Pièce de machine de véhicule et piston - Google Patents

Pièce de machine de véhicule et piston Download PDF

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Publication number
WO2016163244A1
WO2016163244A1 PCT/JP2016/059470 JP2016059470W WO2016163244A1 WO 2016163244 A1 WO2016163244 A1 WO 2016163244A1 JP 2016059470 W JP2016059470 W JP 2016059470W WO 2016163244 A1 WO2016163244 A1 WO 2016163244A1
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WIPO (PCT)
Prior art keywords
layer
heat insulating
insulating layer
piston
protective layer
Prior art date
Application number
PCT/JP2016/059470
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English (en)
Japanese (ja)
Inventor
陽介 田口
松本　晃和
平塚　一郎
誠喜 加藤
大之 小林
恵実 杉澤
新美　拓哉
裕介 猪飼
一騎 佐合
峻 水野
Original Assignee
アイシン精機株式会社
アクロス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2016009495A external-priority patent/JP6339118B2/ja
Application filed by アイシン精機株式会社, アクロス株式会社 filed Critical アイシン精機株式会社
Priority to CN201680020559.8A priority Critical patent/CN107532303B/zh
Priority to EP16776412.5A priority patent/EP3272905B1/fr
Priority to US15/564,052 priority patent/US10487773B2/en
Publication of WO2016163244A1 publication Critical patent/WO2016163244A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C20/00—Chemical coating by decomposition of either solid compounds or suspensions of the coating forming compounds, without leaving reaction products of surface material in the coating
    • C23C20/06—Coating with inorganic material, other than metallic material
    • C23C20/08—Coating with inorganic material, other than metallic material with compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B39/00—Component parts, details, or accessories relating to, driven charging or scavenging pumps, not provided for in groups F02B33/00 - F02B37/00
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F1/00—Cylinders; Cylinder heads 
    • F02F1/24—Cylinder heads
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/10—Pistons  having surface coverings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/10—Pistons  having surface coverings
    • F02F3/12—Pistons  having surface coverings on piston heads

Definitions

  • the present invention relates to a vehicle machine part and a piston.
  • pistons with heat insulation layers are known.
  • a piston in which such a heat insulating layer is formed is disclosed in, for example, International Publication No. 2014/024494.
  • the heat insulating coating film formed on the piston is composed of a heat insulating layer covering the top of the piston and an inorganic coating layer covering the heat insulating layer.
  • the heat insulation layer is composed of a resin and hollow particles embedded in the resin.
  • the inorganic coating layer is composed of an inorganic compound and hollow particles embedded in the inorganic compound. The hollow particles are generally spherical.
  • the inventor of the present application has sufficient heat resistance in the inorganic coating layer containing hollow particles, particularly in the high-temperature environment exceeding about 700 ° C., in the heat insulating coating film formed on the piston of International Publication No. 2014/024494. Therefore, as a result, the inventors have found that the inorganic coating layer is easily peeled off due to the occurrence of cracks in the inorganic coating layer. Therefore, in the piston of International Publication No. 2014/024494, the heat insulation layer having low heat resistance is exposed and deteriorated due to the peeling of the inorganic coating layer in a high temperature environment. There is a problem that it is difficult to ensure the property. Note that in this case, heat efficiency is reduced in the internal combustion engine in which the piston is used because heat easily escapes from the portion of the heat insulating layer deteriorated in the piston, and as a result, the fuel consumption of the internal combustion engine is reduced.
  • the present invention has been made to solve the above-described problems, and one object of the present invention is to provide a vehicle machine component and a piston capable of ensuring high heat insulation even in a high temperature environment. Is to provide.
  • the vehicle mechanical component according to the first aspect of the present invention includes a mechanical component main body, a heat insulating layer formed on the mechanical component main body, an inorganic compound formed on the heat insulating layer and formed from an alkoxide, and an inorganic component. And a protective layer containing scaly inorganic solid particles dispersed in the compound.
  • the inorganic compound formed from the alkoxide and the scaly inorganic solid particles dispersed in the inorganic compound are included on the heat insulating layer.
  • a protective layer is formed. This makes it possible to easily disperse the scaly inorganic solid particles so as to form a layer in the inorganic compound as compared with the case where spherical hollow particles are dispersed in the inorganic compound. Can be suppressed by the scale-like inorganic solid particles laminated in a layered manner even when placed in a high temperature environment.
  • the scale-like inorganic solid particles are made of mica, talc, or wollastonite. If comprised in this way, a scale-like inorganic solid particle can be disperse
  • the inorganic compound of the protective layer is formed of a coupling agent and a binder having an amino group is dispersed, and the amino group of the binder and the heat insulating layer Are combined with other components. If comprised in this way, since the adhesive strength (peeling strength) of a protective layer and a heat insulation layer can be improved, a protective layer and a heat insulation layer can be stuck more firmly.
  • the protective layer further includes a long gap in a lateral direction perpendicular to the thickness direction of the protective layer. If comprised in this way, since the heat insulation in a protective layer can be improved with the space
  • the voids are preferably formed between layers of scale-like inorganic solid particles laminated in the protective layer. If comprised in this way, a space
  • the heat insulating layer is formed on the surface of the mechanical heat insulating layer
  • the second heat insulating layer is formed on the surface of the first heat insulating layer and includes an inorganic compound.
  • a functional group that binds to the constituent components of the second heat insulating layer is provided on the surface of the first heat insulating layer on the second heat insulating layer side by a modification treatment using an organometallic compound. If comprised in this way, the adhesive strength of a 1st heat insulation layer and the 2nd heat insulation layer containing an inorganic compound can be improved with a functional group. Thereby, a 1st heat insulation layer and a 2nd heat insulation layer can be stuck more firmly.
  • the first heat insulating layer and the second heat insulating layer as the heat insulating layer, for example, a material having high adhesion to the machine component main body or a material having high heat insulating property is used as the first heat insulating layer on the machine component main body side.
  • a material having high heat resistance and strength can be used as the binder of the second heat insulating layer on the outer surface side.
  • the heat insulating layer includes a first heat insulating layer formed on the machine component main body and a second heat insulating layer formed on the surface of the first heat insulating layer.
  • the surface of the first heat insulation layer on the second heat insulation layer side is provided with a recess into which the second heat insulation layer enters. If comprised in this way, the adhesion strength of a 1st heat insulation layer and a 2nd heat insulation layer can be improved by a 2nd heat insulation layer entering a recessed part. Thereby, a 1st heat insulation layer and a 2nd heat insulation layer can be stuck more firmly.
  • the heat insulating layer is made of an anodized film layer formed on the surface of the machine part body, and the anodized film layer extends from the surface on the protective layer side.
  • Micropores having a size and nanometer-sized nanopores extending from the surface on the protective layer side, and adjusting the amount of the inorganic compound impregnated into the micropores and the nanopores, the pores of the micropores The rate is configured to be larger than the porosity of the nanopore portion.
  • the inorganic compound impregnated in the micropores and nanopores can be integrated with the inorganic compound in the protective layer by impregnating the micropores and nanopores with the inorganic compound.
  • the anodized film layer and the protective layer can be firmly adhered.
  • the porosity of the micropores is made relatively small, while maintaining the hardness of the anodic oxide coating layer, the micropores Therefore, the thermal conductivity of the anodic oxide coating layer can be reduced.
  • the scale-like inorganic solid particles are dispersed in the inorganic compound so as to be 35% by volume or more and 80% by volume or less. If comprised in this way, a scale-like inorganic solid particle can be reliably disperse
  • the heat insulation layer is formed on the machine component main body, the first heat insulation layer in which the first heat insulation layer hollow particles are dispersed, and the surface of the first heat insulation layer. And a second heat insulating layer. If comprised in this way, the heat insulation of a 1st heat insulation layer can be improved more with the 1st heat insulation layer hollow particle.
  • a primer layer which is disposed between the machine component body and the first heat insulating layer and on the surface of the machine component body and in which the hollow particles and the solid particles are not dispersed. If comprised in this way, since a primer layer can suppress that a hollow particle and a solid particle contact
  • the thickness of the first heat insulating layer and the thickness of the second heat insulating layer are both larger than the thickness of the protective layer and larger than the thickness of the primer layer. If comprised in this way, since the thickness of a 1st heat insulation layer and the thickness of a 2nd heat insulation layer can be enlarged, the heat insulation of a piston can be improved reliably.
  • the second heat insulating layer is dispersed in the heat insulating layer inorganic compound formed from alkoxide or alkali silicate, and the heat insulating layer inorganic compound.
  • Second heat insulating layer hollow particles. If comprised in this way, heat resistance, chemical-resistance, and intensity
  • the thickness of the protective layer is 10 ⁇ m or more and 500 ⁇ m or less. If comprised in this way, the heat resistance in a protective layer can be reliably maintained by making the thickness of a protective layer into 10 micrometers or more. Moreover, it can suppress that stress concentrates in the layer of a protective layer by the thickness of a protective layer being 500 micrometers or less.
  • the piston according to the second aspect of the present invention includes a piston main body, a heat insulating layer formed on the piston main body, an inorganic compound formed on the heat insulating layer and formed from an alkoxide, and a scale dispersed in the inorganic compound. And a protective layer containing inorganic solid particles.
  • a protective layer including an inorganic compound formed from an alkoxide and scale-like inorganic solid particles dispersed in the inorganic compound is formed on the heat insulating layer.
  • FIG. 5 is a schematic diagram showing the periphery of a combustion chamber of an internal combustion engine according to first to third embodiments of the present invention. It is the expanded sectional view showing the coating layer periphery by a 1st embodiment of the present invention. It is the photograph of the surface of Example 1, 2 of the 1st Example performed in order to confirm the effect of this invention, and the comparative example 4.
  • FIG. It is a cross-sectional photograph of the protective layer in Example 1 of the 1st Example performed in order to confirm the effect of this invention. It is a cross-sectional photograph of the protective layer in Example 2 of 1st Example performed in order to confirm the effect of this invention. It is the expanded sectional view which showed the coating layer periphery by 2nd Embodiment of this invention.
  • FIG. 13 is a cross-sectional view showing a periphery of an interface between an alumite layer and a protective layer formed under conditions different from those in FIG. 12 in a piston manufacturing process according to a third embodiment of the present invention.
  • the internal combustion engine 100 As shown in FIG. 1, the internal combustion engine 100 according to the first embodiment of the present invention has a combustion chamber 100a in which fuel burns.
  • the combustion chamber 100a is formed in a space surrounded by the piston 10 constituting the lower part, the cylinder block 20 constituting a part of the side part, and the cylinder head 30 constituting the upper part.
  • the piston 10 includes a piston main body 11 made of an aluminum alloy and a coating layer 40 that is disposed on the top portion 10a of the piston 10 on the combustion chamber 100a side and has high heat insulation (low thermal conductivity).
  • the coating layer 40 prevents heat in the combustion chamber 100a from escaping from the combustion chamber 100a via the piston body 11.
  • the piston 10 and the piston body 11 are examples of the “vehicle machine part” and the “machine part body” of the present invention, respectively.
  • the coating layer 40 is on the surface of the 1st heat insulation layer 41 formed on the surface in the top part 10a of the piston main body 11, and the surface of the 1st heat insulation layer 41.
  • the second heat insulating layer 42 formed and a protective layer 43 formed on the surface of the second heat insulating layer 42 are configured in a three-layer structure.
  • the protective layer 43 constitutes the outermost layer of the coating layer 40 and the piston 10 and is exposed to the combustion chamber 100a side.
  • the thickness t1 of the coating layer 40 is not less than about 31 ⁇ m and not more than about 3100 ⁇ m.
  • the first heat insulating layer 41 and the second heat insulating layer 42 are examples of the “heat insulating layer” in the present invention.
  • the first heat insulating layer 41 is provided to increase the heat insulating property of the piston 10.
  • the first heat insulating layer 41 includes a layer main body portion 41a that mainly forms the first heat insulating layer 41, and a large number of hollow particles 41b dispersed in the layer main body portion 41a.
  • the hollow particles 41b are an example of the “first heat insulating layer hollow particles” in the present invention.
  • the layer body 41a of the first heat insulating layer 41 is preferably made of a material having adhesion, heat resistance, chemical resistance and sufficient strength.
  • Examples of the layer body 41a include epoxy resin, amino resin, polyaminoamide resin, phenol resin, xylene resin, furan resin, silicone resin, polyetherimide, polyethersulfone, polyetherketone, and polyetheretherketone.
  • Organic materials such as polyamideimide, polybenzimidazole, thermoplastic polyimide, and non-thermoplastic polyimide can be used.
  • the heat conductivity of the first heat insulating layer 41 can be further improved because the thermal conductivity is smaller than that of the inorganic material compared to the case of using the inorganic material.
  • the adhesion strength between the first heat insulating layer 41 and the piston main body 11 can be improved.
  • the hollow particles 41b of the first heat insulating layer 41 are particles whose inside is covered with an outer shell, and the thermal conductivity in the hollow portion is small. Thereby, in the 1st heat insulation layer 41 in which many hollow particles 41b were disperse
  • the layer body 41a can be sufficiently secured, so that it is possible to prevent the first heat insulating layer 41 from being formed in a layer shape.
  • the porosity in the 1st heat insulation layer 41 is about 10 volume% or more and about 85 volume% or less.
  • the material of the outer shell of the hollow particles 41b is preferably a ceramic material or an organic material, more preferably silica (silicon dioxide).
  • the thickness t2 of the first heat insulating layer 41 may be a thickness that can sufficiently secure the heat insulating property. Specifically, the thickness t2 of the first heat insulation layer 41 is about 20 ⁇ m or more and about 2000 ⁇ m or less, and preferably about 20 ⁇ m or more and about 1000 ⁇ m or less.
  • the average particle diameter of the hollow particles 41b is preferably smaller than the thickness t2 of the first heat insulating layer 41.
  • the average particle size of the hollow particles 41b is about 1 ⁇ m or more and about 100 ⁇ m or less, and preferably about 1 ⁇ m or more and about 50 ⁇ m or less.
  • the second heat insulating layer 42 is provided to ensure the heat resistance and strength of the coating layer 40 while increasing the heat insulating property of the piston 10.
  • the second heat insulating layer 42 includes a layer main body portion 42a that mainly forms the second heat insulating layer 42, and a large number of hollow particles 42b dispersed in the layer main body portion 42a.
  • the heat insulating properties are improved by dispersing a large number of hollow particles 42 b.
  • the hollow particles 42b of the second heat insulating layer 42 have substantially the same shape and properties as the hollow particles 41b of the first heat insulating layer 41, and the porosity in the second heat insulating layer 42 is the first heat insulating layer. This is substantially the same as the porosity in 41.
  • the hollow particles 42b are an example of the “second heat insulating layer hollow particles” in the present invention.
  • the layer body portion 42a of the second heat insulating layer 42 is made of an inorganic compound made of a metal oxide and formed from an alkali silicate or an alkoxide.
  • alkali silicate for example, sodium silicate (Na 2 SiO 3 )
  • the alkali silicate is subjected to heat treatment or neutralization treatment with acid.
  • an inorganic compound mainly composed of a siloxane bond (—Si—O—Si—) in which silicate ions are polymerized is formed as the layer body 42a.
  • a strong inorganic film is formed as the second heat insulating layer 42.
  • the layer body portion 42a of the second heat insulating layer 42 is formed using silicon alkoxide (Si (OR) 4 : R is a functional group such as an ethyl group)
  • Si (OR) 4 R is a functional group such as an ethyl group
  • a dehydration reaction or dealcoholization reaction is performed by heat treatment.
  • an inorganic compound mainly composed of siloxane bonds is formed as the layer body portion 42a.
  • a strong inorganic film having high heat resistance, chemical resistance and strength is formed as the second heat insulating layer 42.
  • silicon alkoxide, zirconium alkoxide (Zr (OR) 4 ), aluminum alkoxide (Al (OR) 4 ), and cerium alkoxide (Ce (OR) 4 ) can be used alone or in combination.
  • an inorganic compound mainly composed of a covalent bond containing oxygen (—X—O—Y—: X (Y) is any one of Si, Zr, Al, or Ce) is formed as the layer body 42a.
  • X (Y) is any one of Si, Zr, Al, or Ce
  • a strong inorganic film having high heat resistance, chemical resistance and strength is formed as the second heat insulating layer 42.
  • the thickness t3 of the second heat insulating layer 42 may be a thickness that can sufficiently secure the heat insulating property. Specifically, the thickness t3 of the second heat insulating layer 42 is about 10 ⁇ m or more and about 1000 ⁇ m or less, and preferably about 10 ⁇ m or more and about 500 ⁇ m or less. The average particle diameter of the hollow particles 42b is preferably smaller than the thickness t3 of the second heat insulating layer 42.
  • the protective layer 43 is provided to protect the first heat insulating layer 41 and the second heat insulating layer 42 on the inner side (piston body 11 side) from high temperatures.
  • the protective layer 43 is provided so that cracks and the like do not occur even in a high temperature environment exceeding about 700 ° C. (for example, a temperature environment of about 900 ° C.).
  • the protective layer 43 includes a layer main body 43a that mainly forms the protective layer 43 and a large number of inorganic solid particles 43b dispersed in the layer main body 43a.
  • the layer body 43a of the protective layer 43 is composed of an inorganic compound made of a metal oxide formed from an alkoxide such as silicon alkoxide, zirconium alkoxide, aluminum alkoxide, or cerium alkoxide.
  • an alkoxide such as silicon alkoxide, zirconium alkoxide, aluminum alkoxide, or cerium alkoxide.
  • the layer main body 43a of the protective layer 43 is made of an inorganic compound made of a metal oxide formed of an alkoxide as in the first embodiment, water or water is produced as a by-product when the alkoxide is processed. Although alcohol is generated, it can be easily removed from the protective layer 43 by heat treatment. Thereby, it is possible to suppress the foreign matter from remaining in the protective layer 43, and thus the heat resistance of the protective layer 43 can be improved.
  • the inorganic solid particles 43b of the protective layer 43 are formed of inorganic particles that are scale-like and filled with an inorganic material instead of being hollow.
  • the “scale-like” means a scale-like thin piece that is small in the thickness direction and extends on a surface orthogonal to the thickness direction.
  • the inorganic solid particles 43b are composed of scaly talc, mica, and wollastonite.
  • the inorganic solid particles 43b may be composed of any one of talc, mica, and wollastonite, or may be composed of a mixture of any two or all three thereof. .
  • the average particle diameter (average particle diameter on the surface orthogonal to the thickness direction) of the inorganic solid particles 43b is about 1 ⁇ m or more and about 100 ⁇ m or less, and preferably about 1 ⁇ m or more and about 50 ⁇ m or less.
  • Talc means hydrous magnesium silicate (Mg 3 Si 4 O 10 (OH) 2 ), and the specific gravity is about 2.7.
  • Mica means a silicate mineral (KMg 3 (Si 3 Al) O 10 (OH) 2 ) and has a specific gravity of about 2.9.
  • Wollastonite means a silicate mineral (CaSiO 3 ) and has a specific gravity of about 2.9. Further, talc, mica, and wollastonite have sufficient heat resistance without melting or the like even when placed under a temperature condition of about 1000 ° C.
  • the scale-like inorganic solid particles 43b are dispersed so as to form a layer in the layer body 43a.
  • the inorganic solid particles 43b are dispersed in the layer body 43a so as to be about 35% by volume or more and about 80% by volume or less, and as a result, a sufficient amount of the inorganic solid particles 43b is dispersed in the layer body.
  • the inorganic solid particles 43b are stacked in the layer main body portion 43a.
  • the inorganic solid particles 43b dispersed in the layer main body 43a are scaly, the effect on the irregularities (surface roughness) of the surface (outer surface) of the protective layer 43 is that spherical hollow particles are Small compared to the case of being distributed. As a result, the surface of the protective layer 43 is formed smoothly.
  • the thickness t2 of the first heat insulating layer 41 and the thickness t3 of the second heat insulating layer 42 are both larger than the thickness t4 of the protective layer 43.
  • the thickness t2 of the first heat insulation layer 41 is about 20 ⁇ m or more and about 2000 ⁇ m or less, and preferably about 20 ⁇ m or more and about 1000 ⁇ m or less.
  • the thickness t4 of the protective layer 43 is about 10 ⁇ m or more and about 500 ⁇ m or less, and preferably about 10 ⁇ m or more and about 300 ⁇ m or less.
  • a piston body 11 made of an aluminum alloy formed in a predetermined shape by casting or the like is prepared. And as shown in FIG. 2, the 1st heat insulation layer 41 is formed on the surface in the top part 10a of the piston main body 11.
  • hollow particles 41b having a predetermined average particle diameter are added to an organic paint containing a predetermined organic material, and stirred using a stirrer (not shown). At this time, the hollow particles 41b are added so that the porosity of the first heat insulating layer 41 after the formation is about 5% by volume or more and about 90% by volume or less.
  • the organic paint to which the hollow particles 41b are added is applied and baked on the surface of the top 10a of the piston body 11. Thereby, on the surface of the piston main body 11, the 1st heat insulation layer 41 in which the hollow particle 41b was disperse
  • the second heat insulating layer 42 is formed on the surface of the first heat insulating layer 41.
  • hollow particles 42b having a predetermined average particle diameter are added to an aqueous paint containing a predetermined alkali silicate or alkoxide, and the mixture is stirred using a stirrer.
  • the hollow particles 42b are added so that the void ratio of the hollow particles 42b in the formed second heat insulating layer 42 is about 5% by volume or more and about 90% by volume or less.
  • a water-based paint containing an alkali silicate or alkoxide is applied on the surface of the first heat insulating layer 41 and subjected to heat treatment or the like.
  • the heat treatment can be performed at a temperature higher than about 200 ° C. which is the annealing temperature of the aluminum alloy.
  • distributed is formed so that it may become predetermined
  • a protective layer 43 is formed on the surface of the second heat insulating layer 42.
  • scale-like inorganic solid particles 43b having a predetermined average particle diameter are added to an aqueous paint containing a predetermined alkoxide, and stirred using a stirrer.
  • the scale-like inorganic solid particles 43b are added so that the volume ratio of the inorganic solid particles 43b in the formed protective layer 43 is about 35% by volume or more and about 80% by volume or less.
  • a water-based paint to which the scale-like inorganic solid particles 43b are added is applied on the surface of the second heat insulating layer 42 and subjected to heat treatment or the like.
  • the protective layer 43 in which the scaly inorganic solid particles 43b are dispersed is formed on the surface of the second heat insulating layer 42 so as to have a predetermined thickness t4.
  • the piston 10 in which the coating layer 40 as shown in FIG. 1 is formed on the top portion 10a is manufactured.
  • the layer main body portion 43a made of an inorganic compound formed from an alkoxide and the layer main body portion 43a are dispersed.
  • the protective layer 43 including the scaly inorganic solid particles 43b is formed.
  • the protective layer 43 can be prevented from being peeled off, so that the first heat insulating layer 41 and the second heat insulating layer 42 can be maintained by the protective layer 43 even in a high temperature environment.
  • the piston 10 It is possible to ensure high heat insulation. Therefore, since it is possible to suppress the heat from being easily escaped from the piston 10, it is possible to suppress a decrease in the thermal efficiency of the internal combustion engine 100 in which the piston 10 is used, and as a result, the fuel consumption of the internal combustion engine 100 is improved. Can be made.
  • the scale-like inorganic solid particles 43b are made of mica, talc, or wollastonite, thereby making it easier to form a layer in the layer main body 43a. Inorganic solid particles 43b can be dispersed.
  • the first heat insulating layer 41 including the layer main body 41a made of an organic material and the second heat insulating layer 42 including the layer main body 42a made of an inorganic material are provided.
  • the adhesion strength and heat insulating properties with the piston main body 11 can be improved, and the outer surface (combustion chamber 100a).
  • the heat resistance and strength can be improved by using an inorganic material for the layer main body portion 42a of the second heat insulating layer 42 on the) side.
  • characteristics such as heat resistance and heat insulation of the piston 10 can be effectively improved.
  • the scale-like inorganic solid particles 43b are dispersed in the protective layer 43 so as to be about 35% by volume or more and about 80% by volume or less. Thereby, the scale-like inorganic solid particles 43b can be reliably dispersed so as to form a layer in the layer main body 43a.
  • the 1st heat insulation layer 41 has the layer main-body part 41a and the hollow particle 41b disperse
  • the second heat insulating layer 42 includes a layer main body portion 42a formed from an inorganic compound formed from an alkoxide or alkali silicate, and hollow particles 42b dispersed in the layer main body portion 42a.
  • a layer main body portion 42a formed from an inorganic compound formed from an alkoxide or alkali silicate, and hollow particles 42b dispersed in the layer main body portion 42a.
  • strength can be improved with the layer main-body part 42a which consists of an inorganic compound, improving heat insulation with the hollow particle 42b.
  • the protective layer 43 is disposed so that the layer main body 43a is positioned between the stacked inorganic solid particles 43b. Since it can be formed, the structure of the protective layer 43 can be strengthened. Thereby, the thickness t4 of the protective layer 43 can be easily increased.
  • the heat resistance in the protective layer 43 can be reliably maintained by setting the thickness t4 of the protective layer 43 to about 10 ⁇ m or more. Further, when the thickness t4 of the protective layer 43 is set to about 500 ⁇ m or less, it is possible to prevent stress from being concentrated in the layer of the protective layer 43.
  • Example 1 (Configuration of Examples and Comparative Examples) First, the piston 10 (see FIG. 1) of Example 1 was produced. Note that an aluminum alloy equivalent to AC8A-T6 (specified in JIS 5202) was used as the aluminum alloy constituting the piston body 11, and formed into a predetermined shape by casting.
  • the composition of the aluminum alloy corresponding to AC8A-T6 is as follows: Si: 11 mass% to 13 mass%, Cu: 2.5 mass% to 4.0 mass%, Mg: 0.5 mass% to 1.2 mass% % By mass or less, Ni: 1.75% by mass to 3.0% by mass, Fe: 0.5% by mass or less, Zn: 0.15% by mass or less, Mn: 0.15% by mass or less, Ti: 0.00%.
  • the 1st heat insulation layer 41 was formed on the surface in the top part 10a of the piston main body 11.
  • hollow particles 41b having an outer shell made of silica and having an average particle diameter of 19.76 ⁇ m were added to an organic paint containing N-methyl-2-pyrrolidone and stirred using a stirrer.
  • the weight of the organic paint was set to 100, the hollow particles 41b were added to the organic paint so that the weight of the hollow particles 41b was 130%.
  • the organic coating material with which the hollow particle 41b was added was apply
  • distributed in the layer main-body part 41a was formed on the surface of the piston main body 11.
  • the first heat insulating layer 41 was formed to have a thickness t1 of 100 ⁇ m.
  • the porosity in the 1st heat insulation layer 41 was 78 volume%.
  • a second heat insulating layer 42 was formed on the surface of the first heat insulating layer 41.
  • the hollow particles 42b were added to an aqueous paint (so-called water glass) containing sodium silicate as an alkali silicate, and stirred using a stirrer.
  • the weight of the water-based paint was set to 100
  • the hollow particles 42b were added to the water-based paint so that the weight of the hollow particles 42b was 95%.
  • the aqueous coating material to which the hollow particle 42b was added was apply
  • the 2nd including the layer main-body part 42a which consists of an inorganic compound mainly comprised from the silicic acid, and many hollow particles 42b disperse
  • a heat insulating layer 42 was formed.
  • the second heat insulating layer 42 was formed to have a thickness t3 of 100 ⁇ m.
  • the porosity in the 2nd heat insulation layer 42 was 80 volume%.
  • a protective layer 43 was formed on the surface of the second heat insulating layer 42.
  • inorganic solid particles 43b composed of talc and having an average particle size of 5.61 ⁇ m are added to an aqueous coating material containing silicon alkoxide and zirconium alkoxide as alkoxide, and stirred using a stirrer. did. And the water-based coating material with which the inorganic solid particle 43b was added was apply
  • the protective layer 43 containing was formed on the surface of the second heat insulating layer 42.
  • the protective layer 43 containing was formed on the surface of the second heat insulating layer 42.
  • the protective layer 43 was formed to have a thickness t4 of 20 ⁇ m.
  • the inorganic solid particles 43b were dispersed in the protective layer 43 so as to be 65% by volume. Thereby, the piston 10 of Example 1 was produced.
  • Example 2 was performed in the same manner as Example 1 except that inorganic solid particles 43b composed of mica and having an average particle size of 5.82 ⁇ m were used as the inorganic solid particles.
  • a piston 10 was prepared.
  • nano hollow particles having an outer shell composed of silica and having an average particle diameter of 0.108 ⁇ m were added to an organic paint containing N-methyl-2-pyrrolidone and stirred using a stirrer. . At this time, the nano hollow particles were added to the organic paint so that the weight of the nano hollow particles was 14% when the weight of the organic paint was 100. And the organic coating material with which nano hollow particle was added was apply
  • distributed in the layer main-body part was formed on the surface of the piston main body.
  • the first heat insulating layer was formed to have a thickness of 125 ⁇ m.
  • the porosity in the 1st heat insulation layer was 15 volume%.
  • a piston was produced in the same manner as in Example 1 except that a protective layer was formed using hollow particles instead of inorganic solid particles.
  • a piston formed up to the second heat insulating layer in the same manner as in Example 1 was prepared.
  • nano hollow particles having an outer shell made of silica and having an average particle diameter of 0.108 ⁇ m were added to the water-based paint, and stirred using a stirrer.
  • the nano hollow particles were added to the organic paint so that the weight of the nano hollow particles became 7% when the weight of the water-based paint was 100.
  • the aqueous coating material with which the nano hollow particle was added was apply
  • a protective layer including a layer main body portion made of an inorganic compound mainly composed of silicic acid and a large number of hollow particles dispersed in the layer main body portion was formed on the surface of the second heat insulating layer.
  • the protective layer was formed to a thickness of 20 ⁇ m.
  • the porosity in the nano hollow particles was 12% by volume.
  • heat resistance, thermal conductivity, and surface roughness were measured using test materials corresponding to the pistons of Examples 1 and 2 and Comparative Examples 1 to 4.
  • the temperature at which cracks start to be confirmed when held for 10 minutes was defined as the temperature (° C.) as an index of heat resistance.
  • the heat resistance was measured in increments of 50 ° C.
  • the surface state of the test material corresponding to each piston of Examples 1 and 2 and Comparative Example 4 when held at 900 ° C. for 10 minutes was observed.
  • the thermal conductivity is 0.11 (W / m ⁇ K), which is about the same as that in Comparative Example 4 in both Examples 1 and 2, and the thermal conductivity is not different from that in Comparative Example 3. It was obtained and was significantly smaller than Comparative Examples 1 and 2. Thereby, it was confirmed that the thermal conductivity can be sufficiently reduced in both the pistons 10 of Examples 1 and 2 and the heat insulation can be improved.
  • the surface roughness (Ra) was 0.60 in both Examples 1 and 2, which was smaller than Comparative Examples 3 and 4 and significantly smaller than Comparative Examples 1 and 2. As a result, the surface roughness was sufficiently small in both Examples 1 and 2, and it was confirmed that the possibility of knocking in the pistons 10 in Examples 1 and 2 was sufficiently reduced. On the other hand, in Comparative Example 2, the surface roughness (Ra) was excessively large as 38, and as a result, it was confirmed that the possibility of knocking in the piston of Comparative Example 2 was quite high.
  • the structure of the piston 110 by 2nd Embodiment of this invention is demonstrated.
  • the piston 110 according to the second embodiment in addition to the piston 10 according to the first embodiment, an example in which the layers and the adhesion strength between the first heat insulating layer 141 and the piston main body 11 are improved will be described.
  • the same structure as the said 1st Embodiment attaches
  • the piston 110 is an example of the “vehicle machine part” in the present invention.
  • the piston 110 As shown in FIG. 1, the piston 110 according to the second embodiment of the present invention includes a piston body 11 made of an aluminum alloy, and a coating layer 140 having high heat insulation (low thermal conductivity).
  • the coating layer 140 includes a primer layer 144 formed on the surface of the top portion 10 a of the piston body 11 and a first layer formed on the surface of the primer layer 144.
  • the heat insulating layer 141 includes a four-layer structure including a first heat insulating layer 141, a second heat insulating layer 142 formed on the surface of the first heat insulating layer 141, and a protective layer 143 formed on the surface of the second heat insulating layer 142.
  • the first heat insulating layer 141 and the second heat insulating layer 142 are examples of the “heat insulating layer” in the present invention.
  • the primer layer 144 is provided in order to improve the adhesion between the piston body 11 and the first heat insulating layer 141.
  • the primer layer 144 includes a layer body portion 144a, but does not contain hollow particles or solid particles. Thereby, since the contact area of the piston main body 11 and the 1st heat insulation layer 141 via the primer layer 144 can be improved, it is possible to improve the adhesive strength of the 1st heat insulation layer 141 and the piston main body 11. is there.
  • the ratio of the contact area between the piston main body 11 and the first heat insulating layer 141 via the primer layer 144 (the piston main body 11 and the first heat insulating layer 141).
  • the ratio of the contact area to the area facing the heat insulating layer 141 is preferably about 60% or more.
  • the thickness t5 of the primer layer 144 is preferably as small as possible as long as the adhesion strength between the first heat insulating layer 141 and the piston body 11 can be sufficiently improved. Specifically, the thickness t5 of the primer layer 144 is about 10 ⁇ m or more and about 100 ⁇ m or less.
  • the first heat insulating layer 141 and the second heat insulating layer 142 are respectively similar to the first heat insulating layer 41 and the second heat insulating layer 42 of the first embodiment, and the layer main body portions 41a and 42a, and a large number of hollow particles 41b and 42b.
  • the layer main body portion 144a of the primer layer 144 and the layer main body portion 41a of the first heat insulating layer 141 are made of the same material. preferable.
  • a plurality of fine concave portions 141c are formed on the surface of the first heat insulating layer 141 on the second heat insulating layer 142 side.
  • the shear resistance increases, and the first heat insulating layer 141 and the second heat insulating layer 142 are prevented from being displaced in a parallel direction along the interface.
  • the adhesion between the first heat insulating layer 141 and the second heat insulating layer 142 is improved.
  • the diameter D1 of the opening on the second heat insulating layer 142 side of the recess 141c is about 10 ⁇ m or more and about 500 ⁇ m or less, and preferably about 10 ⁇ m or more and about 100 ⁇ m or less. Furthermore, the diameter D1 is more preferably about 30 ⁇ m or more and about 70 ⁇ m or less. Moreover, it is preferable that the space
  • the recess 141c is formed such that the inner surface is inclined so that the inner diameter of the bottom part on the primer layer 144 side is larger than the diameter D1 of the opening on the second heat insulating layer 142 side. Thereby, the shear resistance can be further increased.
  • a functional group that binds to the constituent components of the layer main body portion 42a of the second heat insulating layer 142 is formed on the surface of the first heat insulating layer 141 on the second heat insulating layer 142 side by the modification treatment using the organometallic compound.
  • the surface of the first heat insulating layer 141 including the flat surface of the first heat insulating layer 141 and the inner surfaces of the plurality of formed recesses 141c has a hydroxy group (--Si—OH) or the like containing a silanol group (—Si—OH). OH), a carbonyl group (—C ⁇ O), a carboxyl group (—COOH), and other functional groups are formed.
  • This functional group is incorporated in a covalent bond containing oxygen to form a covalent bond with the inorganic compound of the second heat insulating layer 142, or forms a hydrogen bond with the covalent oxygen of the second heat insulating layer 142.
  • the functional group on the surface of the first heat insulation layer 141 is formed by a modification process in which a combustion flame in which an organometallic compound containing Si (a special modifier) is mixed is sprayed on the surface of the first heat insulation layer 141.
  • the protective layer 143 includes the layer main body 43a and a large number of inorganic solid particles 43b, like the protective layer 43 of the first embodiment.
  • a binder having an amino group (—NH 2 ) is dispersed in an inorganic compound made of a metal oxide formed using alkoxide.
  • the binder is formed from an amino-based coupling agent such as aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, and enters a part of the siloxane bond when the layer is formed.
  • the binder containing an amino group which is a polar group and easily forms a hydrogen bond is dispersed in the layer main body 43a of the protective layer 143.
  • the amino group of the binder is oxygen and hydrogen in a covalent bond (—X—O—Y—: X (Y) is any one of Si, Zr, Al, or Ce) that is a component in the protective layer 143.
  • a bond is formed, or a hydrogen bond is formed with oxygen in a covalent bond (—X—O—Y—) that is a constituent component of the second heat insulating layer 142.
  • strength of the protective layer 143 and the adhesiveness of the 2nd heat insulation layer 142 and the protective layer 143 are improved.
  • the thickness t2 of the first heat insulation layer 141 and the thickness t3 of the second heat insulation layer 142 are both larger than the thickness t4 of the protective layer 143 and larger than the thickness t5 of the primer layer 144.
  • the thickness t4 of the protective layer 143 is larger than the thickness t5 of the primer layer 144.
  • the other structure of 2nd Embodiment is the same as that of the said 1st Embodiment.
  • the piston body 11 is prepared. And as shown in FIG. 6, the organic coating material containing a predetermined organic material is apply
  • a plurality of fine concave portions 141c having a predetermined size are formed on the surface of the first heat insulating layer 141 with a predetermined interval L1 by laser processing that irradiates a laser.
  • a reforming process is performed in which a combustion flame mixed with an organometallic compound containing Si (a special modifier) is sprayed on the surface of the first heat insulating layer 141.
  • the treatment time for blowing the combustion flame to the entire first heat insulating layer 141 is about 5 seconds or more and about 50 seconds or less.
  • the structural component of the layer main body portion 42a of the second heat insulating layer 142 is formed on the surface of the first heat insulating layer 141 (on the flat surface and the inner surface of the plurality of recessed portions 141c) by the reforming process using the organometallic compound. Is formed.
  • the second heat insulating layer 142 is formed on the surface of the first heat insulating layer 141 in the same manner as in the first embodiment. At this time, a part of the second heat insulating layer 142 enters the recess 141 c of the first heat insulating layer 141. Furthermore, the functional group formed on the surface of the first heat insulating layer 141 is incorporated into a covalent bond containing oxygen to form a covalent bond with the inorganic compound of the second heat insulating layer 142 or the covalent bond of the second heat insulating layer 142. Or form hydrogen bonds with oxygen.
  • a protective layer 143 is formed on the surface of the second heat insulating layer 142.
  • scale-like inorganic solid particles 43b having a predetermined average particle diameter and an amino-based coupling agent are added to an aqueous paint containing a predetermined alkoxide, followed by stirring using a stirrer. To do.
  • the weight of the water-based paint to which the scale-like inorganic solid particles 43b are added is 100, the weight of the amino coupling agent is about 0.1% or more and about 10% or less. Add an amino coupling agent.
  • a water-based paint containing an alkoxide and an amino coupling agent is applied on the surface of the second heat insulating layer 142, and heat treatment is performed.
  • the protective layer 143 in which the scale-like inorganic solid particles 43 b are dispersed is formed on the surface of the second heat insulating layer 142.
  • a binder having an amino group is dispersed in the layer main body 43a (inorganic compound) of the protective layer 143.
  • Each of the amino groups of the binder includes a covalent bond containing oxygen which is a constituent component in the protective layer 143 (—X—O—Y—: X (Y) is any of Si, Zr, Al, or Ce).
  • a hydrogen bond is formed with oxygen in the inner layer, or a hydrogen bond is formed with oxygen in the covalent bond (—X—O—Y—) that is a constituent component of the second heat insulating layer 142.
  • the piston 110 having the coating layer 140 formed on the top portion 10a as shown in FIG. 1 is manufactured.
  • the layer main body 43a made of an inorganic compound formed from an alkoxide is dispersed on the first heat insulating layer 141 and the second heat insulating layer 142, and dispersed in the layer main body 43a.
  • the protective layer 143 including the scaly inorganic solid particles 43b is formed.
  • the amino group of the binder formed from the coupling agent is a covalent bond (which is a constituent component of the second heat insulating layer 142).
  • a hydrogen bond is formed with oxygen in —X—O—Y—).
  • a functional group that binds to the constituent components of the second heat insulating layer 142 is provided on the surface of the first heat insulating layer 141 on the second heat insulating layer 142 side by a modification process using an organometallic compound. .
  • the adhesive strength between the first heat insulating layer 141 and the second heat insulating layer 142 containing the inorganic compound can be improved by the functional group, the first heat insulating layer 141 and the second heat insulating layer 142 are more firmly adhered to each other. Can be made.
  • the concave portion 141c into which the second heat insulating layer 142 enters is provided on the surface of the first heat insulating layer 141 on the second heat insulating layer 142 side.
  • the adhesion strength of the 1st heat insulation layer 141 and the 2nd heat insulation layer 142 can be improved by the 2nd heat insulation layer 142 entering into the recessed part 141c.
  • the 1st heat insulation layer 141 and the 2nd heat insulation layer 142 can be stuck more firmly.
  • the primer which has the layer main-body part 144a in which the hollow particle and the solid particle are not disperse
  • Layer 144 is disposed. Accordingly, the primer layer 144 can prevent the hollow particles and the solid particles from coming into direct contact with the piston main body 11, so that the first heat insulating layer 141 and the piston main body 11 are bonded via the primer layer 144. The area can be surely increased.
  • the thickness t2 of the first heat insulating layer 141 and the thickness t3 of the second heat insulating layer 142 are both larger than the thickness t4 of the protective layer 143 and larger than the thickness t5 of the primer layer 144. To do. Thereby, since the thickness t2 of the 1st heat insulation layer 141 and the thickness t3 of the 2nd heat insulation layer 142 can be enlarged, the heat insulation of the piston 110 can be improved reliably.
  • the remaining effects of the second embodiment are similar to those of the aforementioned first embodiment.
  • composition of AC8A-T6 is as follows: Si: 11 mass% to 13 mass%, Cu: 0.8 mass% to 1.3 mass%, Mg: 0.7 mass% to 1.3 mass%, Ni: 0.8 mass% or more and 1.5 mass% or less, Fe: 0.8 mass% or less, Zn: 0.15 mass% or less, Mn: 0.15 mass% or less, Ti: 0.20 mass% or less Cr: 0.10% by mass or less, Sn: 0.05% by mass or less, Pb: 0.05% by mass or less, Al: remainder.
  • hollow particles 41b having an outer shell made of silica and having an average particle diameter of 19.76 ⁇ m were added to an organic paint containing N-methyl-2-pyrrolidone and stirred using a stirrer. . At this time, the hollow particles 41b were added to the organic paint so that the weight would be 130% when the weight of the organic paint was 100. And the organic coating material with which the hollow particle 41b was added was apply
  • a plurality of fine concave portions 141c were formed on the surface of the first heat insulating layer 141 by laser processing that irradiates laser.
  • the recess 141c was formed to have an opening D1 of 30 ⁇ m and a depth H of 36 ⁇ m.
  • a plurality of recesses 141c were formed at intervals L1 of 500 ⁇ m. Then, the modification process which sprays the combustion flame which mixed the organometallic compound (special modifier) containing Si on the surface of the 1st heat insulation layer 141 was performed.
  • the surface component of the first heat insulating layer 141 (on the flat surface and the inner surface of the plurality of recessed portions 141c) is combined with the constituent components of the layer main body portion 42a of the second heat insulating layer 142.
  • a functional group was formed.
  • the second heat insulating layer 142 was formed on the surface of the first heat insulating layer 141 in the same manner as the second heat insulating layer 42 of Example 1 of the first example. Thereby, the test material 1 was produced.
  • test material 2 was produced in the same manner as the test material 1 except that the laser processing and the modification treatment were not performed.
  • a cross-cut test was performed on the test materials 1 and 2. Specifically, according to the old JIS K5400, cuts were formed in an X shape on the surfaces of the second heat insulation layers of the test materials 1 and 2. Thereafter, the pressure-sensitive adhesive tape was strongly pressure-bonded to the cut portion and then peeled off at a predetermined angle to observe the state of the X-shaped cut.
  • the adhesion between the first heat insulating layer 141 and the second heat insulating layer 142 can be improved by the concave portion 141c formed by the laser processing process and the functional group formed by performing the modification process. It was confirmed that.
  • the active functional group was formed in the resin containing polyimide with low polarity on the surface of the first heat insulating layer 141 by the modification treatment, the wettability between the surface of the first heat insulating layer 141 and the water-based paint is improved. As a result, it is considered that the adhesion between the first heat insulating layer 141 and the second heat insulating layer 142 is improved.
  • a protective layer 143 was formed on the surface of the second heat insulating layer 142.
  • inorganic solid particles 43b composed of talc having an average particle size of 5.61 ⁇ m and aminopropyltriethoxysilane as an amino coupling agent are added to a water-based paint containing alkoxide. The mixture was stirred using a stirrer. At this time, the amino coupling agent was added so that the weight of the amino coupling agent was 5% when the weight of the water-based paint to which the scale-like inorganic solid particles 43b were added was 100. did.
  • the aqueous coating material to which the inorganic solid particle 43b was added was apply
  • the protective layer 143 was formed to have a thickness t4 of 20 ⁇ m. Further, the inorganic solid particles 43b were dispersed in the protective layer 143 so as to be 65% by volume. Thereby, the test material 3 was produced.
  • test material 4 was produced in the same manner as the test material 3 except that an amino coupling agent was not added.
  • a cross-cut test was performed on the test materials 3 and 4. Specifically, in accordance with JIS K5600, cuts were formed in a lattice shape on the surface of each protective layer of the test materials 3 and 4. Thereafter, the pressure-sensitive adhesive tape was strongly pressure-bonded to the cut portion and then peeled off at a predetermined angle to observe the state of the grid-like cut.
  • adhesion strength measurement test ⁇ Configuration of test material>
  • the adhesion strength of each interface was specifically confirmed.
  • the same test material as the test materials 1 to 4 used in the above-described crosscut test and cross cut test was used as a test material.
  • a test material 1a was produced in the same manner as the test material 1 except that only the laser processing was performed and the modification treatment was not performed.
  • the test material 1b was produced like the test material 1 except performing only the modification process and not performing the laser processing.
  • Test materials 5a, 5b, 5c, and 5d were prepared in the same manner as the test material 3, except that isocyanatopropyltrimethoxysilane was added as a coupling agent of loxypropyltrimethoxysilane and isocyanate.
  • a primer layer on a predetermined base material is used as a test material.
  • the test material 6 in which 144 and the 1st heat insulation layer 141 were formed in this order was prepared.
  • the primer layer 144 of the second embodiment was formed on the surface of a predetermined base material made of an AC8A-T6 aluminum alloy plate corresponding to the piston body 11.
  • an organic paint containing N-methyl-2-pyrrolidone was applied onto the surface of a predetermined substrate and baked.
  • the primer layer 144 that includes the layer main body portion 143a made of a resin containing polyimide but does not contain hollow particles and solid particles was formed. At this time, the primer layer 144 was formed to have a thickness t5 of 15 ⁇ m. Then, the 1st heat insulation layer 141 was formed on the surface of the primer layer 144 like the 1st heat insulation layer 41 of Example 1 of the said 1st Example. Thereby, the test material 6 was produced.
  • test material 7 was produced in the same manner as the test material 6 except that no primer layer was formed.
  • the surface roughness (Ra) is 6 to 4 with respect to the region where the predetermined layer (primer layer, first heat insulating layer and second heat insulating layer) of the predetermined base material is formed.
  • a milling process was performed so as to be 10 and an alumite process was performed without performing a sealing process. Further, a groove having a depth of about 1 mm was formed on the surface of the outermost layers (first heat insulating layer, second heat insulating layer and protective layer) of the test materials 1 to 6, 1a, 1b and 5a to 5d.
  • an adhesion strength measurement test was performed on the test materials 1 to 6, 1a, 1b and 5a to 5d using a thin film adhesion strength measuring apparatus.
  • the bottom part of the cylindrical pin (outer diameter: 7.1 mm) of the thin film adhesion strength measuring apparatus was bonded to a region surrounded by a groove formed on the surface of the outermost layer of the test material.
  • the outermost layer of the test material was peeled off by pulling up at a constant speed (20 mm / sec) while applying a tensile load of 1030N.
  • the strength (MPa) when the outermost layer was peeled was defined as the adhesion strength.
  • each test material 8 was prepared in the same manner as the test material 3, and the adhesion strength was measured, and the change in the adhesion strength was graphed.
  • adhesion strength test As a result of the adhesion strength test (adhesion strength test of test materials 1, 1a, 1b and 2) at the interface between the first heat insulation layer and the second heat insulation layer shown in Table 2, at least one of laser processing and modification treatment In the test materials 1, 1 a, and 1 b in which either of them was performed, the adhesion strength was clearly higher than that of the test material 2 in which neither the laser processing nor the modification treatment was performed. Furthermore, in the test material 1 subjected to both the laser processing and the modification treatment, it is twice as large as the adhesion strength of the test materials 1a and 1b subjected to either the laser processing or the modification treatment. The adhesion strength increased.
  • the concave portion formed by the laser processing and the functional group formed by the modification treatment can improve the adhesion strength between the first heat insulating layer and the second heat insulating layer, and the concave portion and the functional group can be improved. By forming both, it was confirmed that an adhesion strength nearly twice as high as that obtained when only one of the concave portion and the functional group was formed was obtained.
  • adhesion strength test (adhesion strength test of test materials 3, 4 and 5a to 5d) at the interface between the second heat insulating layer and the protective layer shown in Table 3, any type of coupling agent is protected.
  • the adhesion strength was clearly higher than that of the test material 4 in which the coupling agent was not added to the protective layer.
  • the adhesion strength was increased nearly three times.
  • the functional group (amino group (—NH 2 ), vinyl group (—CH ⁇ CH 2 ), epoxy group (3-membered ether), methacryl group (CH 2 ⁇ C (CH) formed by the coupling agent. 3 )
  • the binder having —CO—) and the isocyanate group (—N ⁇ C ⁇ O) With the binder having —CO—) and the isocyanate group (—N ⁇ C ⁇ O)), the adhesion strength between the second heat insulating layer and the protective layer can be improved, and with the binder having an amino group. It was confirmed that particularly high adhesion strength was obtained.
  • an amino group is a polar group and can form a hydrogen bond with various elements, it is thought that the adhesiveness of a 2nd heat insulation layer and a protective layer improved more.
  • the adhesion strength test adheresion strength test of the test materials 6 and 7 at the interface between the predetermined base material (piston main body) and the first heat insulation layer shown in Table 4, the predetermined base material and the first heat insulation In the test material 6 in which the primer layer was formed at the interface with the layer, the adhesion strength was increased nearly three times compared to the adhesion strength of the test material 7 in which the primer layer was not formed.
  • the adhesion area of a predetermined base material and a 1st heat insulation layer improves, and it is possible to improve the adhesiveness of a predetermined base material and a 1st heat insulation layer more. I was able to confirm.
  • the second heat insulating layer can be obtained by adding an amino coupling agent to the water-based paint at a weight ratio of 0.1% to 10%. It was confirmed that the adhesion strength between the protective layer and the protective layer can be improved. In addition, it was confirmed that the adhesion strength between the second heat insulating layer and the protective layer can be increased to 8 MPa or more by adding an amino coupling agent to the water-based paint by 3 to 6% by weight. .
  • the piston 210 As shown in FIGS. 1 and 10, the piston 210 according to the third embodiment of the present invention includes a piston main body 11 made of an aluminum alloy and a coating layer 240 having high heat insulation (low thermal conductivity). .
  • the coating layer 240 is formed on the alumite layer 241 formed on the surface of the top portion 10a of the piston body 11 and the surface 241e of the alumite layer 241 as shown in FIGS.
  • a two-layer structure is formed with the formed protective layer 243.
  • the anodized layer 241 is an example of the “heat insulating layer” and “anodized film layer” in the present invention.
  • the anodized layer 241 is formed by performing an anodic oxidation treatment among the chemical conversion treatments on the aluminum alloy constituting the piston main body 11. That is, the alumite layer 241 is mainly composed of an aluminum oxide (alumina) having a lower thermal conductivity than the aluminum alloy. Thereby, the alumite layer 241 has higher heat insulation than the piston body 11 made of an aluminum alloy. Furthermore, since the piston body 11 and the alumite layer 241 are integrally formed, the adhesion strength between the piston body 11 and the alumite layer 241 is large.
  • the protective layer 243 includes a layer main body portion 43a that mainly forms the protective layer 243, and scale-like inorganic solid particles 43b dispersed in the layer main body portion 43a.
  • a large number of fine cells 241d mainly composed of alumina are formed from the surface 241e on the protective layer 243 side (Z1 side) of the anodized layer 241 toward the Z2 side. It extends in the thickness direction (Z direction). Between the cells 241d, nanopore portions 241f having a nanometer size pore diameter D2 are formed. The nanopore portion 241f extends in the thickness direction from the surface 241e.
  • the diameter W of the cell 241d is about 25 nm or more and about 300 nm or less, and preferably about 50 nm or more and about 300 nm or less. Further, the pore diameter D2 of the nanopore part 241f is about 10 nm or more and about 350 nm or less, and preferably about 50 nm or more and about 250 nm or less.
  • the micropores 241g extending in the thickness direction from the surface 241e and the in-layer micropores that are formed in the layer of the alumite layer 241 and do not communicate with the micropores 241g.
  • a portion 241h is formed.
  • the micro hole portion 241g has a micrometer size hole diameter D3. Specifically, the hole diameter D3 is not less than about 1 ⁇ m and not more than about 3 ⁇ m.
  • the ratio of the total of the nanopore portion 241f, the micropore portion 241g, and the in-layer micropore portion 241h is about 5% or more and about 80% or less.
  • the pore abundance ratio (%) is defined as the area occupied by the sum of the nanopores 241f, the micropores 241g, and the in-layer micropores 241h in a predetermined cross section of the alumite layer 241 of the alumite layer 241. It is possible to calculate by dividing by the area of the cross section and multiplying by 100.
  • a part of the nanopore 241f and a part of the micropore 241g of the alumite layer 241 are impregnated with an inorganic compound constituting the layer main body 43a of the protective layer 243. (Intrusion).
  • the alumite layer 241 is protected by the inorganic compound of the protective layer 243, so that embrittlement of the alumite layer 241 is suppressed and the adhesion strength between the alumite layer 241 and the protective layer 243 is improved.
  • the hardness of the anodized layer 241 is also improved.
  • the inorganic compound is mainly impregnated so as to fill the whole nanopore part 241f.
  • the inorganic compound is mainly impregnated only in the vicinity of the surface 241e of the micropore 241g. This is because the liquid (the aqueous paint described below) is more likely to flow through the inside of the nanopore 241f than the micropore 241g due to capillary action.
  • the remainder of the nanopore 241f not impregnated with the inorganic compound and the remainder of the micropore 241g not impregnated with the inorganic compound are voids.
  • the in-layer micropores 241h are not impregnated with an inorganic compound and are voids.
  • the space formed in these alumite layers 241 has a low thermal conductivity, so that the heat insulation of the alumite layer 241 is improved.
  • the ratio (porosity) of the micropores 241g impregnated with the inorganic compound is the nanopores 241f formed in the alumite layer 241. It is larger than the ratio (porosity) of the nanopore part 241f impregnated with the inorganic compound.
  • the porosity (%) is the cross-sectional area occupied by the inorganic compound existing in the micropore 241g (nanopore 241f) in the predetermined cross section of the alumite layer 241. It is a value obtained by dividing by the cross-sectional area of the hole 241f) and multiplying by 100.
  • the porosity of the micropore part 241g is about 30% or more and about 45% or less.
  • the porosity of the nanopore portion 241f is preferably about 10% or more and about 20% or less.
  • the thickness t6 of the alumite layer 241 is about 10 ⁇ m or more and about 1000 ⁇ m or less.
  • the thickness t6 of the alumite layer 241 is preferably about 30 ⁇ m or more. Thereby, it is possible to ensure sufficient heat insulation of the alumite layer 241.
  • the thickness t6 of the alumite layer 241 is preferably about 500 ⁇ m or less, and more preferably about 200 ⁇ m or less. Thereby, it is possible to suppress the formation time of the alumite layer 241 from being long.
  • the protective layer 243 is formed by positioning the layer body 43a made of an inorganic compound between the scale-like inorganic solid particles 43b stacked in the thickness direction (Z direction). .
  • a plurality of voids 243c extending in the lateral direction (Y direction) orthogonal to the thickness direction (Z direction) are formed in the protective layer 243.
  • the voids 243c are formed between the layers of the scale-like inorganic solid particles 43b where the layer main body 43a is not disposed.
  • the space 243c improves the heat insulation in the protective layer 243.
  • gap 243c in the protective layer 243 is about 1.5% or more and about 5% or less.
  • gap 243c should just be formed so that it may extend in the horizontal direction as a whole. That is, the gap 243 may have some portions extending in the thickness direction.
  • the length L2 in the lateral direction (Y direction) orthogonal to the thickness direction (Z direction) of the gap 243c is about 5 ⁇ m or more. Moreover, it is preferable that the length L2 of the space
  • the thickness t7 of the protective layer 243 is about 10 ⁇ m or more and about 500 ⁇ m or less. By setting the thickness t7 of the protective layer 243 to about 10 ⁇ m or more, the heat resistance in the protective layer 243 can be reliably maintained. By setting the thickness t7 of the protective layer 243 to about 500 ⁇ m or less, it is possible to suppress stress concentration in the protective layer 243.
  • the thickness t7 of the protective layer 243 is preferably about 300 ⁇ m or less. Accordingly, it is possible to effectively suppress stress concentration in the protective layer 243, and thus a good protective layer 243 can be maintained.
  • a binder having an amino group (—NH 2 ) may be dispersed in the inorganic compound of the layer main body 43a formed using alkoxide.
  • the heat resistance of the coating layer 240 is about 1000 ° C., and the physical properties can be sufficiently maintained even at the top portion 10 a of the piston body 11 that becomes high temperature when placed in the internal combustion engine 100.
  • the thermal conductivity of the coating layer 240 is preferably about 0.6 W / m ⁇ K or less, and more preferably about 0.5 W / m ⁇ K or less.
  • the specific heat per unit volume of the coating layer 240 is preferably about 1900 kJ / m 3 ⁇ K or less, and more preferably about 1800 kJ / m 3 ⁇ K. Further, the specific heat per unit volume of the coating layer 240 is more preferably about 1700 kJ / m 3 ⁇ K or less.
  • the remaining configuration of the third embodiment is similar to that of the aforementioned first embodiment.
  • the piston body 11 is prepared. And the anodizing process as a chemical conversion process is performed with respect to the surface in the top part 10a (refer FIG. 1) of the piston main body 11.
  • FIG. Specifically, the piston body 11 is placed in a treatment liquid containing an acid such as sulfuric acid, oxalic acid, or phosphoric acid in a state where the surface other than the surface of the top 10a of the piston body 11 is masked. Then, a predetermined voltage is applied for a predetermined time between an electrode (not shown) disposed in the processing liquid and the piston body 11 while maintaining the processing liquid at a predetermined temperature. As a result, as shown in FIG.
  • the aluminum on the surface of the piston body 11 is oxidized, and an alumite layer 241 is formed on the surface of the piston body 11.
  • the nanopore 241f is formed in the alumite layer 241 so as to extend in the thickness direction (Z direction).
  • the micropore portion 241g or the in-layer micropore portion is formed.
  • 241 h is formed in the alumite layer 241.
  • a treatment for enlarging the pore diameter D2 of the nanopore portion 241f and the pore diameter D3 of the micropore portion 241g may be performed.
  • the treatment for enlarging the hole diameter is performed by immersing the piston body 11 for a predetermined time in a treatment liquid containing an acid such as phosphoric acid.
  • a treatment liquid containing an acid such as phosphoric acid.
  • the alumite layer 241 may be formed so that the pore diameter D2 of the nanopore 241f is increased, or as shown in FIG. 14, the pore diameter D2 of the nanopore 241f is reduced.
  • An anodized layer 241 may be formed.
  • a protective layer 243 is formed on the surface 241 e of the alumite layer 241.
  • a scale-like inorganic solid particle 43b having a predetermined average particle diameter and a predetermined solvent for example, isopropyl alcohol or polyethylene glycol
  • a predetermined solvent for example, isopropyl alcohol or polyethylene glycol
  • an amino coupling agent may be added to the water-based paint.
  • the viscosity of the aqueous paint is adjusted by adjusting the amount of the solvent added to the aqueous paint.
  • the viscosity of the water-based paint is preferably about 5 mPa ⁇ s or more and about 15 mPa ⁇ s or less.
  • the solvent is added so that the weight of the solvent is about 20% or more and about 50% or less when the weight of the water-based paint to which the scale-like inorganic solid particles 43b are added is 100.
  • the protective layer 243 in which the scaly inorganic solid particles 43b are dispersed is formed on the surface 241e of the alumite layer 241.
  • the scale-like inorganic solid particles 43b are laminated in layers, whereby the layer main body 43a (inorganic compound) is positioned between the inorganic solid particles 43b as shown in FIG.
  • the strong protective layer 243 is comprised by the layer main-body part 43a and the inorganic solid particle 43b.
  • a plurality of voids 243c extending in the lateral direction (Y direction) orthogonal to the thickness direction (Z direction) are formed in a region where the layer main body portion 43a is not located among the layers of the inorganic solid particles 43b.
  • the liquid component excluding the scale-like inorganic solid particles 43b in the aqueous paint is impregnated inside the nanopores 241f and the micropores 241g of the alumite layer 241.
  • the nanopore portion 241f the movement of the aqueous paint due to the capillary phenomenon is large, and as a result, the aqueous paint is easily impregnated so as to fill the entire nanopore portion 241f.
  • the micropore part 241g having a larger pore diameter than the nanopore part 241f the movement of the aqueous paint due to the capillary phenomenon is small.
  • the ratio (porosity) of the micropores 241g into which the inorganic compound derived from the water-based paint has entered is the nanopores formed in the alumite layer 241. It becomes larger than the ratio (porosity) of the nanopore part 241f in which the inorganic compound has entered among 241f.
  • the viscosity of the water-based paint when the viscosity of the water-based paint is adjusted to about 15 mPa ⁇ s, the water-based paint hardly moves inside the nanopore 241f and the micropore 241g. Thereby, as shown in FIG. 12, in the nanopore part 241f and the micropore part 241g, the proportion of voids (porosity) into which the inorganic compound does not enter increases. On the other hand, when the viscosity of the water-based paint is adjusted to about 5 mPa ⁇ s, the water-based paint easily moves inside the nanopores 241f and the micropores 241g. Thereby, as shown in FIG.
  • the viscosity of the water-based paint may be greater than about 15 mPa ⁇ s or less than about 5 mPa ⁇ s.
  • a binder having an amino group is dispersed in the layer main body 43a (inorganic compound) of the protective layer 243.
  • Each of the amino groups of the binder includes a covalent bond containing oxygen which is a constituent component in the protective layer 243 (—X—O—Y—: X (Y) is any of Si, Zr, Al, or Ce).
  • a hydrogen bond is formed with oxygen in the inner layer, or a hydrogen bond is formed with oxygen in the covalent bond (—Al—O—Al—) of alumina constituting the alumite layer 241.
  • the layer main body portion 43a made of an inorganic compound formed from an alkoxide, and the scaly inorganic solid particles dispersed in the layer main body portion 43a 43b is formed.
  • the alumite layer 241 can be maintained by the protective layer 243 also in a high temperature environment, As a result, high heat insulation can be ensured in the piston 210.
  • the protective layer 243 is provided with a plurality of gaps 243c extending in the lateral direction (Y direction) orthogonal to the thickness direction (Z direction).
  • the heat insulation in the protective layer 243 can be improved by the space
  • the gap 243c is long in the lateral direction, the gap 243c having a low thermal conductivity can be positioned over a wider range in the lateral direction of the protective layer 243 compared to the gap long in the thickness direction.
  • the thermal conductivity of the layer 243 can be reduced over a wide range.
  • the gap 243c is formed between the scale-like inorganic solid particles 43b stacked in the protective layer 243. Thereby, the space
  • the inorganic compound impregnated in the micropores 241g and the nanopores 241f and the inorganic compound of the protective layer 243 are obtained. Since they can be integrated, embrittlement of the anodized layer 241 can be suppressed, and the anodized layer 241 and the protective layer 243 can be firmly adhered to each other.
  • the porosity of the micropore 241g is made larger than the porosity of the nanopore 241f.
  • Example 3 (Characteristic evaluation) ⁇ Configuration of Examples and Comparative Examples> First, the piston 210 (see FIG. 1) of Example 3 was produced. As the aluminum alloy constituting the piston body 11, the same aluminum alloy as the AC8A-T6 equivalent aluminum alloy used in the first embodiment was used and formed into a predetermined shape by casting.
  • an alumite layer 241 was formed on the surface of the top portion 10 a of the piston body 11.
  • the piston body 11 was placed in a 30 g / L oxalic acid solution (treatment liquid) in a state where the surface other than the surface of the top portion 10a of the piston body 11 was masked.
  • the constant voltage of 100V was applied between the electrode (not shown) arrange
  • aluminum on the surface of the piston body 11 was oxidized to form an alumite layer 241 on the surface of the piston body 11.
  • the alumite layer 241 was formed so that the thickness t6 of the alumite layer 241 was in the range of 50 to 60 ⁇ m.
  • a protective layer 243 was formed on the surface 241e of the alumite layer 241.
  • inorganic solid particles 43b composed of mica and having an average particle diameter of 5.82 ⁇ m and isopropyl alcohol are added to an aqueous coating material containing silicon alkoxide and zirconium alkoxide as alkoxide.
  • the mixture was stirred using a stirrer.
  • the viscosity of the water-based paint after stirring was adjusted to 5 mPa ⁇ s.
  • the water-based coating material with which the inorganic solid particle 43b was added was apply
  • the layer main body 43a made of an inorganic compound mainly composed of silicic acid and zirconia, and a large number of inorganic solid particles 43b dispersed in the layer main body 43a.
  • a protective layer 243 including this was formed.
  • the protective layer 243 was formed so that the thickness t7 of the protective layer 243 was in the range of 20 to 30 ⁇ m.
  • the inorganic solid particles 43b were dispersed in the protective layer 243 so as to be 65% by volume. Thereby, the piston 210 of Example 3 was produced.
  • the pistons of comparative examples 3 and 4 of the first embodiment described above were used. Furthermore, the piston of Comparative Example 5 was produced. Unlike the piston 210 of Example 3, the piston of Comparative Example 5 is not formed with a protective layer. That is, in the piston of Comparative Example 5, the alumite layer was formed so that the thickness was in the range of 50 to 60 ⁇ m, but the protective layer was not formed.
  • the cross section of the formed piston 210 of Example 3 was observed.
  • the micropore portion 241g and the in-layer micropore portion 241h were formed in the alumite layer 241.
  • a part of the micropore portion 241g and the in-layer micropore portion 241h are not impregnated with the inorganic compound constituting the protective layer 243, and as a result, voids are formed in the alumite layer 241.
  • gap 243c was formed between the layers of the scale-like inorganic solid particle 43b laminated
  • the gap 243c was formed to extend in the lateral direction perpendicular to the thickness direction. Further, it was confirmed that the ratio (void ratio) of the voids 243c in the protective layer 243 was in the range of 1.5% to 5%.
  • the cross section of the coating layer is cut based on the standard of JIS Z2244, and the Vickers hardness of the heat insulating layer (polyimide layer in Comparative Examples 3 and 4 and anodized layer in Comparative Example 5 and Example 3). was measured.
  • variety is given by measuring several places.
  • each of the pistons of Example 3 and Comparative Examples 3 to 5 was mounted on an internal combustion engine.
  • each of the pistons of Example 3 and Comparative Examples 3 to 6 was mounted on a single cylinder engine as an internal combustion engine. Then, the engine was driven so that the rotation speed was 2200 rpm and the combustion pressure was 4.4 MPa. And after driving the engine for 10 hours, the coating layer formed on the surface of the piston was observed.
  • Example 3 As a result, as shown in Table 5, the heat resistance of Example 3 was 1000 ° C., and it was confirmed that sufficient heat resistance was ensured. On the other hand, in Comparative Examples 3 and 4, the heat resistance was 750 ° C. or less, and it was confirmed that sufficient heat resistance was not ensured.
  • Example 3 was in the range of 14 to 15 MPa, which was clearly greater than the adhesion strength of Comparative Examples 3 to 5 (7 MPa or less). Furthermore, when Example 3 and Comparative Example 5 were compared, the adhesion strength increased more than three times due to the provision of the protective layer 243. In Example 3, since the inorganic compound constituting the protective layer 243 was impregnated in the anodized layer 241, the adhesion strength between the protective layer 243 and the anodized layer 241 was improved. Furthermore, since the alumite layer 241 and the piston body 11 are integrally formed by anodizing, the adhesion strength between the alumite layer 241 and the piston body 11 is high. As a result, it is considered that the adhesion strength of the coating layer 240 has increased.
  • Comparative Example 5 although the adhesion strength between the alumite layer and the piston main body is high, the protective layer is not formed, and therefore, delamination occurs in the alumite layer, resulting in a decrease in the adhesion strength of the coating layer. it is conceivable that.
  • Example 3 the Vickers strength of Example 3 was in the range of 100 to 120 Hv, which was clearly higher than the Vickers strength of Comparative Examples 3 to 5 (70 Hv or less). This is because, in Example 3, the alumite layer 241 itself has a hardness higher than that of the resin constituting the heat insulating layer of Comparative Examples 3 and 4, and the inorganic compound constituting the protective layer 243 is the anodized layer 241 as described above. It is considered that the hardness in the alumite layer 241 is increased due to the point of impregnation inside.
  • Example 3 in both the 10-hour endurance performance and the 100-hour endurance performance, the coating layer 240 had almost no defects, and the piston 210 was usable.
  • Comparative Examples 3 and 4 did not have 10-hour durability performance, and Comparative Example 5 had insufficient 10-hour durability performance. This is because the adhesion between the protective layer 243 and the alumite layer 241 is achieved in addition to the fact that the protective layer 243 is reliably maintained by dispersing the scaly inorganic solid particles 43b in the protective layer 243. It is considered that the long-term durability of the coating layer 240 was improved in Example 3 due to the improvement.
  • the alumite layer of the coating layer exposed outside has become embrittled by the combustion pressure of an engine. From this, it was confirmed that the long-term durability of the coating layer 240 can be improved by forming the protective layer 243 of Example 3 on the surface 241e of the alumite layer 241.
  • Example 4 a piston 210 was produced in the same manner as in Example 3 except that the viscosity of the aqueous paint after stirring was adjusted to 10 mPa ⁇ s.
  • Example 5 a piston 210 was produced in the same manner as in Example 3 except that the viscosity of the aqueous paint after stirring was adjusted to 15 mPa ⁇ s.
  • Comparative Example 6 while changing the conditions of the anodizing treatment with respect to Example 3, unlike Example 3, a piston having a protective layer formed using polysilazane was produced. Specifically, an alumite layer was formed by anodizing the piston body made of an aluminum alloy equivalent to AC8A-T6. At this time, the thickness of the alumite layer was in the range of 30 to 40 ⁇ m. Thereafter, a 20% polysiloxane solution was applied on the surface of the anodized layer and heat-treated. Here, in Comparative Example 6, no scaly inorganic solid particles were added to the polysiloxane solution.
  • the protective layer containing the layer main-body part which consists of an inorganic compound mainly comprised from the silicic acid was formed on the surface of an alumite layer by repeating the process of this application
  • the heat resistance was measured under the same conditions as in the first example. Further, using test materials corresponding to the pistons of Examples 3 to 5 and Comparative Example 6, the porosity of the micropores and the porosity of the nanopores in the alumite layer, the thermal conductivity and the unit volume in the coating layer The specific heat per unit was measured. The thermal conductivity and specific heat per unit volume were measured by a flash method and a DSC method, respectively. In addition, since the porosity of the micropores, the porosity of the nanopores, the thermal conductivity, and the specific heat per unit volume are measured using a plurality of test materials, the values have a wide range.
  • Example 3 and Comparative Example 6 were both 1000 ° C., and it was confirmed that sufficient heat resistance was ensured.
  • the thickness of the protective layer in Comparative Example 6 is 1 to 5 ⁇ m, which is very small.
  • the protective layer is formed by repeating application and heat treatment in Comparative Example 6, an interface is formed in the protective layer, and as a result, the protective layer of Comparative Example 6 is a continuous film. It is not considered. Therefore, in the piston of the comparative example 6, peeling is likely to occur in the protective layer, and as a result, the piston of the comparative example 6 has temporary heat resistance, but maintains heat resistance for a long period of time. It is considered difficult to do.
  • the porosity of the micropores of Comparative Example 6 was 20 to 25%, while the porosity of the micropores of Examples 3 to 5 was increased to 30% or more. Further, the porosity of the nanopore portion of Comparative Example 6 was 5 to 8%, while the porosity of the micropore portion of Examples 3 to 5 was increased to 10% or more.
  • the area occupied by the voids in the coating layer was larger than that in Comparative Example 6. This is because, compared with Comparative Example 6 using a polysiloxane solution, in Examples 3 to 5, the micropores and nanopores could be reliably formed with regions (holes) not impregnated with the inorganic compound. It is thought that.
  • the porosity of the micropores was larger than the porosity of the nanopores. This is presumably because the water-based paint was easily impregnated into the nanopores by capillary action.
  • Comparative Example 6 is 1.4 to 1.6 (W / m ⁇ K), while the thermal conductivity of Examples 3 to 5 is 0.6 (W / m ⁇ K). It became smaller below. As a result, it was confirmed that the coating layers of Examples 3 to 5 were less likely to release heat compared to Comparative Example 6.
  • the specific heat per unit volume of Comparative Example 6 is 3500 to 3700 (kJ / m 3 ⁇ K), while the specific heat per unit volume of Examples 3 to 5 is 1900 (kJ / m 3 ⁇ K). It became smaller below.
  • the porosity of the micropore 241g and the porosity of the nanopore 241f increased as the viscosity of the water-based paint increased. This is because, as the viscosity of the water-based paint increases, the water-based paint becomes difficult to move inside the micropores 241g and nanopores 241f, and as a result, the waterborne paint is contained in the micropores 241g and nanopores 241f. This is considered to be because the amount of impregnation with (inorganic compound) decreased. Thus, it was confirmed that the porosity of the alumite layer 241 can be adjusted by adjusting the viscosity of the water-based paint.
  • the thermal conductivity and specific heat per unit volume decreased as the viscosity of the water-based paint increased. This is considered to be due to the fact that the area occupied by the voids in the coating layer 241 has increased.
  • a desired coating having both high strength and heat insulation can be obtained by adjusting the conditions of the anodizing treatment and the viscosity of the water-based paint in consideration of the balance between the strength reduction of the coating layer 241 due to voids and the improvement of heat insulation. It is believed that layer 241 can be formed.
  • the configuration of the present invention may be applied to a vehicle machine part that requires heat resistance and heat insulation.
  • the configuration of the present invention may be applied to a turbocharger 310 mounted on a vehicle as in a first modification of the present invention shown in FIG.
  • the coating layer 40 of the first embodiment and the first layer are formed on the inner surface (shaded portion in FIG. 18) of the passage portion 312 through which high-temperature exhaust gas downstream of the turbine wheel 311 flows.
  • the coating layer 140 according to the second embodiment or the coating layer 240 according to the third embodiment may be formed.
  • the configuration of the present invention may be applied to a jet engine 410 mounted on a vehicle as in a second modification of the present invention shown in FIG.
  • the coating layer 40, 140, or 240 is formed on the inner surface (shaded portion in FIG. 19) of the passage portion 412 through which the high-temperature compressed air downstream of the turbine 411 flows.
  • the turbocharger 310 and the jet engine 410 are examples of the “vehicle machine part” in the present invention.
  • the passage portions 312 and 412 are examples of the “mechanical component body” of the present invention.
  • the heat insulating layer may be only one layer.
  • the heat insulating layer 41 and the protective layer 43 may be provided, and the second heat insulating layer may not be provided.
  • the heat insulating layer may have a layer structure of three or more layers.
  • the layer main body portion 41a of the first heat insulating layer 41 (141) is made of an organic material.
  • the present invention is not limited to this.
  • the layer main-body part of a 1st heat insulation layer from an inorganic material it is possible to improve intensity
  • the layer main-body part 144a of the primer layer 144 and the layer main-body part 41a of the 1st heat insulation layer 141 were both comprised from the organic material, this invention is limited to this. Absent.
  • one of the layer main body portion of the first heat insulating layer and the layer main body portion of the primer layer may be composed of an inorganic material, and the other may be composed of an organic material.
  • the layer main body portion of the first heat insulating layer and the layer main body portion of the primer layer are preferably the same type of material.
  • the layer main body portion of the first heat insulating layer is an inorganic material
  • the layer main body portion of the primer layer is also preferably an inorganic material
  • the layer main body portion of the first heat insulating layer is an organic material
  • the layer body of the primer layer is also preferably an organic material.
  • an amino coupling agent is used as a coupling agent to be added to the protective layer, but the present invention is not limited to this. In this invention, you may use coupling agents other than an amino type as a coupling agent added to a protective layer.
  • vinyl coupling agents such as vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, and epoxy coupling agents such as glycidoxypropyltrimethoxysilane and glycidoxypropyltriethoxysilane
  • Methacrylic coupling agents such as methacryloxypropyltriethoxysilane and methacryloxypropyltrimethoxysilane
  • isocyanate coupling agents such as isocyanatopropyltriethoxysilane and isocyanatopropyltrimethoxysilane may also be used.
  • the adhesion between the second heat insulating layer and the protective layer is as follows. It is possible to improve the property.
  • the concave portion 141c is formed in the first heat insulating layer 141 by laser processing, but the present invention is not limited to this.
  • the recess is formed by removing a part of the surface of the first heat insulating layer by laser processing or the like. The formation is preferable because the shear resistance can be increased.
  • the piston body (machine component body) 11 is made of an aluminum alloy.
  • the machine part main body may be made of a metal material other than an aluminum alloy, or may be made of an organic material such as a resin.
  • the mechanical component body needs to be made of a metal material that can be anodized.
  • a gap may be provided in the protective layer as in the third embodiment.
  • the present invention is not limited to this.
  • the heat insulation layer which consists of organic materials on the surface of an alumite layer.
  • the porosity of the micropores and nanopores in the alumite layer is adjusted by adjusting the viscosity of the organic paint for forming the heat insulating layer, as in the third embodiment. It is possible.
  • Piston (Vehicle machine parts) 11 Piston body (machine part body) 41, 141 First heat insulation layer (heat insulation layer) 41b Hollow particles (first heat insulating layer hollow particles) 42, 142 Second heat insulation layer (heat insulation layer) 42b Hollow particles (second heat insulating layer hollow particles) 43, 143, 243 Protective layer 43b Inorganic solid particles 141c Recess 144 Primer layer 241 Anodized layer (heat insulation layer, anodic oxide coating layer) 241e (protective layer side) surface 241f Nanopores 241g Micropores 243c Air gap 310 Turbocharger (machine parts for vehicles) 410 Jet engine (vehicle machine parts) 312, 412 passage (machine part body)

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)

Abstract

L'invention porte sur une pièce de machine de véhicule, pourvue de : un corps de pièce de machine ; une couche d'isolation thermique formée sur le corps de pièce de machine ; et une couche protectrice formée sur la couche d'isolation thermique et comprenant un composé inorganique formé à partir d'un alcoolate et de particules inorganiques lamellaires dispersées dans le composé inorganique.
PCT/JP2016/059470 2015-04-08 2016-03-24 Pièce de machine de véhicule et piston WO2016163244A1 (fr)

Priority Applications (3)

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CN201680020559.8A CN107532303B (zh) 2015-04-08 2016-03-24 车辆用机械部件及活塞
EP16776412.5A EP3272905B1 (fr) 2015-04-08 2016-03-24 Pièce de machine de véhicule et piston
US15/564,052 US10487773B2 (en) 2015-04-08 2016-03-24 Vehicle mechanical component and piston

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JP2016009495A JP6339118B2 (ja) 2015-04-08 2016-01-21 車両用機械部品およびピストン
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Cited By (5)

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WO2018197338A1 (fr) * 2017-04-28 2018-11-01 Mahle International Gmbh Piston pour moteur à combustion interne
US10578049B2 (en) 2017-04-28 2020-03-03 Mahle International Gmbh Thermal barrier coating for engine combustion component
CN111032341A (zh) * 2017-08-14 2020-04-17 日产自动车株式会社 隔热部件
WO2020142645A1 (fr) * 2019-01-04 2020-07-09 Tenneco Inc. Piston pourvu d'une surface sous-couronne dotée d'un revêtement isolant et procédé de fabrication
WO2023002834A1 (fr) * 2021-07-21 2023-01-26 アート金属工業株式会社 Film isolant thermique et élément isolant thermique

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WO2014024494A1 (fr) * 2012-08-10 2014-02-13 アイシン精機株式会社 Moteur et piston

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JPH06316787A (ja) * 1993-04-28 1994-11-15 Kojundo Chem Lab Co Ltd アルマイトの表面処理法
WO2014024494A1 (fr) * 2012-08-10 2014-02-13 アイシン精機株式会社 Moteur et piston

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018197338A1 (fr) * 2017-04-28 2018-11-01 Mahle International Gmbh Piston pour moteur à combustion interne
US10578049B2 (en) 2017-04-28 2020-03-03 Mahle International Gmbh Thermal barrier coating for engine combustion component
CN111032341A (zh) * 2017-08-14 2020-04-17 日产自动车株式会社 隔热部件
EP3670178A4 (fr) * 2017-08-14 2020-07-01 Nissan Motor Co., Ltd. Composant de protection thermique
CN111032341B (zh) * 2017-08-14 2022-07-12 日产自动车株式会社 隔热部件
US11433637B2 (en) 2017-08-14 2022-09-06 Nissan Motor Co., Ltd. Heat shield component
WO2020142645A1 (fr) * 2019-01-04 2020-07-09 Tenneco Inc. Piston pourvu d'une surface sous-couronne dotée d'un revêtement isolant et procédé de fabrication
WO2023002834A1 (fr) * 2021-07-21 2023-01-26 アート金属工業株式会社 Film isolant thermique et élément isolant thermique

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